JP2000128944A - Water-dispersible compound having alkoxysilane group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compound capable of forming a stable water-in-oil type or an oil-in-water type dispersion after mixing with water and providing a smooth transparent coating by reacting a polyisocyanate component with a specific alkoxysilane group-containing amino compound. SOLUTION: (A) A polyisocyanate component having 2.4 minimal average functional value and containing >=50 wt.% of a polyisocyanate adduct is reacted with (B) an amino compound represented by the formula H(R1)N(CH2)nSi(X)3 [Xs are each an organic group inert to isocyanate group at <100 deg.C and at least one thereof is an alkoxy; R1 is an organic group inert to the isocyanate group at <=100 deg.C; (n) is 1-8] (e.g. N-phenylaminopropyltrimethoxysilane) to afford the objective compound. The above compound contains 1-6 wt.% of an alkoxysilane and further chemically introducing hydrophilic groups sufficient to form a stable dispersion using water without substantially containing the isocyanate group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water-dispersible compound containing alkoxysilane groups and substantially free of isocyanate groups, and its use in aqueous one-component coating compositions.

[0002]

BACKGROUND OF THE INVENTION Alkoxysilanes containing amino groups are key components for linking conventional polymer chemistry and silicone chemistry. The alkoxysilane groups are crosslinked by "silane polycondensation" in the presence of moisture, and the amino groups are introduced into polymers such as polyurethanes, polyureas, and the like. U. S. No. 5,364,955 discloses that an amino-functional silane is first reacted with a maleic acid or fumarate to form a secondary amino group (ie, aspartate) and then incompatible in the reaction product; It is stated that these aspartates can be reacted with NCO prepolymers without encountering heterogeneity or very high viscosity. Co-pending applications (U.S. Pat.
S. Serial No. 08 / 814,561) discloses the reaction of aspartate with monomeric polyisocyanates or polyisocyanate adducts to form compounds containing urea and alkoxysilane groups. One use of these compounds is to mix them with water alone or with other compounds containing alkoxysilane groups to form stable sol-gel formulations. These formulations require that water hydrolyze the silyl ether groups to form hydroxysilanes. This terminal Si-OH group is subsequently converted to Si-O-
Crosslinking is possible through a condensation reaction that forms Si bonds, resulting in a polysiloxane network. However, when trying to mix the compounds described in the co-pending application with water, a stable dispersion is not formed.

[0003]

The object of the present invention is to provide compounds containing alkoxysilane groups which can be mixed with water to form stable water-in-oil or oil-in-water dispersions,
And 2) to provide the compound which cures to form a smooth transparent coating. It is a further object of the present invention to provide alkoxysilane group-containing hydrophilic compounds that can be cured by silane polycondensation to form coatings, sealants and adhesives. These objects can be achieved by using the alkoxysilane group-containing water-dispersible compound of the present invention described below. These compounds can be prepared by reacting a polyisocyanate component with a compound containing a secondary amino group and an alkoxysilane group.

[0004]

The present invention provides an alkoxysilane group content (S) of 1 to 6% by weight, based on the weight of the compound.
i, calculated as molecular weight 28) and containing substantially enough chemically introduced hydrophilic groups to form a stable dispersion using water, substantially free of isocyanate groups, The alkoxysilane group has: a) a minimum average functionality of 2.4 and at least 50
A polyisocyanate component containing by weight polyisocyanate adducts;

Embedded image Wherein X is the same or different and is an organic group inert to an isocyanate group at a temperature lower than 100 ° C., provided that at least one of these groups is an alkoxy group;
₁ is an organic group inert to an isocyanate group at a temperature of 100 ° C. or lower, and n is an integer of 1 to 8]. The invention also relates to the use of these compounds in the preparation of coatings, sealants and adhesives.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The compounds of the present invention are based on the reaction products of polyisocyanates, aminofunctional silanes, and compounds containing hydrophilic groups such as nonionic, anionic and / or cationic groups. And Silanes are introduced via the formation of urea groups, while hydrophilic groups are preferably introduced via the formation of urethane groups. The compounds of the present invention are substantially free of isocyanate groups, ie, contain less than 0.1% by weight of isocyanate groups, based on the weight of the compound.

In suitable compounds containing an alkoxysilane group and an amino group, in formula 1, X is the same or different and is an organic group which is inert to isocyanate groups below 100 ° C., provided that these groups are At least one is an alkoxy or acyloxy group, preferably 1 to 4
R ₁ is an alkyl or alkoxy group having 10 carbon atoms, more preferably an alkoxy group.
An organic group inert to isocyanate groups at 0 ° C. or lower, preferably an alkyl, cycloalkyl or aromatic group having 1 to 12, more preferably 1 to 8 carbon atoms, or a compound of the formula II- (CH ₂ ) a group corresponding to _n- Si- (X) ₃ (II), wherein n is 1 to 8, preferably 2 to
It is an integer of 4, more preferably an integer of 3. Particularly preferred are compounds wherein X is methoxy, ethoxy or propoxy, more preferably methoxy or ethoxy, more preferably methoxy and n is 3.

Examples of suitable aminoalkylalkoxysilanes of the formula I containing a secondary amino group include N-phenylaminopropyltrimethoxysilane (OSI Speci).
alties, available from Witco as A-9669), bis- (γ-trimethoxysilylpropyl) amine (OSI Specialties, available as A-1170 from Witco), N-cyclohexylaminopropyltriethoxy-silane, N -Methylaminopropyltrimethoxysilane and the corresponding alkyldiethoxysilane and dimethoxysilane.

A special group of compounds containing alkoxysilane groups is that which also contains aspartate groups, such as those of the formula III

Embedded image Wherein X and n are as described above, and Z is C
OOR ₅ or an aromatic ring, preferably COOR ₅ ,
₂ and R ₅ are the same or different and are organic groups inert to an isocyanate group at 100 ° C. or lower, preferably an alkyl group having 1 to 9 carbon atoms, more preferably methyl, ethyl or R ₃ and R ₄ are the same or different and are hydrogen or an organic group which is inert to the isocyanate group at 100 ° C. or less, and is preferably hydrogen.]

The compound of the formula III is prepared by converting an aminoalkylalkoxysilane corresponding to the formula IV H ₂ N— (CH ₂ ) _n —Si— (X) ₃ (IV) to the formula V Z—CR ₃ ＣＲCR ₄ —COOR It is prepared by reacting maleic acid, fumaric acid or cinnamic acid ester corresponding to ₂ (V).

Suitable aminoalkylalkoxysilanes of formula IV include 2-aminoethyl-dimethylmethoxy-silane; 6-aminohexyl-tributoxysilane; 3-aminopropyl-trimethoxysilane; 3-aminopropyl-triethoxysilane Silane; 3-aminopropyl-methyldiethoxysilane; 5-aminopentyl-trimethoxysilane; 5-aminopentyl-triethoxysilane and 3-aminopropyl-triisopropoxysilane. 3-Aminopropyl-trimethoxysilane and 3-aminopropyl-triethoxysilane are particularly preferred.

[0011] Suitable substituted esters of maleic acid, fumaric acid or cinnamic acid which are suitable for use in the preparation of polyaspartate include dimethyl, diethyl, dibutyl (eg di-n-butyl), Mixed esters based on diamil, di-2-ethylhexyl ester and mixtures thereof with other alkyl groups of maleic acid and fumaric acid; methyl, ethyl and butyl esters of cinnamic acid; and methyl at the 2 and 3 positions And the corresponding maleic, fumaric and cinnamic esters substituted with. The dimethyl ester of maleic acid is preferred, and the diethyl and dibutyl esters are particularly preferred. The primary amine is reacted with an ester of maleic acid, fumaric acid or cinnamic acid to form the formula
It is known to form aspartate of III. S. No. 5,364,955, which is incorporated herein by reference. The preparation of aspartate is carried out, for example, at a temperature of from 0 to 100 ° C. using the starting materials in a proportion such that at least one, preferably one olefinic double bond is present for each primary amino group. Done. Excess starting material may be removed by distillation after the reaction. A solvent may or may not be used in the reaction, but the use of a solvent is less preferred. If a solvent is used, dioxane is an example of a suitable solvent.

The compound containing an alkoxysilane group and an amino group is used in an amount of 1 to 6% by weight, preferably 2 to 6% by weight, more preferably 2 to 5% by weight, based on the weight of the compound of the present invention. (Calculated as Si, molecular weight 28). The compounds of the formula III are colorless to pale yellow. These react with the polyisocyanates to form the compounds containing alkoxysilane groups of the present invention without further purification. According to the present invention, a special type of urea group formed by the reaction of a compound containing an alkoxysilane group and an aspartate group with a polyisocyanate component can form the compound by a known method at a high temperature in the presence of an appropriate catalyst. By heating to
It can be converted to a hydantoin group. Thus, the term "urea group" is also intended to include compounds containing N-CO-N groups, such as hydantoin groups.

The polyisocyanate component for preparing the compounds of the present invention has a minimum average functionality of 2.4, preferably 2.6, more preferably 2.8, and 6,
Preferably it has a maximum average functionality of 5. The polyisocyanate component may contain a monomeric diisocyanate or a polyisocyanate adduct having a functionality that does not meet these requirements, provided that the average functionality of the polyisocyanate component meets these requirements. The polyisocyanate component comprises at least 50% by weight, preferably at least 70% by weight, more preferably at least 95% by weight.
% By weight of isocyanurate, uretdione, biuret, urethane, allophanate, carbodiimide and / or
Or oxadiazine-triones, preferably containing isocyanurate, uretdione, biuret and / or allophanate groups. In addition to the polyisocyanate adduct, the polyisocyanate component may optionally contain either monomeric polyisocyanates or other polyisocyanate adducts.

Suitable monomeric diisocyanates which may be present in monomeric form in the polyisocyanate component or which may be used to prepare the polyisocyanate adduct are of the formula R (NCO) _{2 where} R is the molecular weight Represents a residue obtained by removing an isocyanate group from about 112 to 1,000, preferably about 140 to 400, of an organic diisocyanate]. Diisocyanates suitable for the process of the present invention are those wherein R is
Divalent aliphatic hydrocarbon groups having 4 to 40, preferably 4 to 18 carbon atoms, divalent alicyclic hydrocarbon groups having 5 to 15 carbon atoms, 7 to 15 carbon atoms Having a divalent araliphatic hydrocarbon group or an aromatic group having 6 to 15 carbon atoms.

Examples of suitable organic diisocyanates include:
1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,1
2-dodecamethylene diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-2-isocyanatomethylcyclopentane, 1
-Isocyanato-3-isocyanato-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis- (4-isocyanatocyclohexyl) -methane, 2,4'-dicyclohexyl-methane diisocyanate, 1,3- and 1,4-bis- (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methyl-cyclohexyl) -methane,
α, α, α ′, α′-tetramethyl-1,3- and / or -1,4-xylylenediisocyanate, 1-isocyanato-1-methyl-4 (3) -isocyanatomethylcyclohexane, 2,4 -And / or 2,6-hexahydrotoluylene diisocyanate, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or
Or 2,6-toluylene diisocyanate, 2,4- and / or 4,4'-diphenyl-methane diisocyanate, 1,5-diisocyanatonaphthalene, and mixtures thereof.

Monomeric polyisocyanates containing three or more isocyanate groups, such as 4-isocyanatomethyl-1,8-octamethylene diisocyanate, and aromatic polyisocyanates such as 4,4 ', 4 "-
Triphenylmethane triisocyanate and polyphenylpolymethylene polyisocyanate obtained by phosgenating an aniline / formaldehyde condensate may also be present as a polyisocyanate component,
Alternatively, it may be used to prepare a polyisocyanate adduct. Preferred organic diisocyanates include
1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis- (4-isocyanatocyclohexyl) -methane, 1-isocyanato- 1-methyl-4
(3) -isocyanatomethylcyclohexane, 2,4-
And / or 2,6-toluylene diisocyanate, and 2,4- and / or 4,4'-diphenyl-methane diisocyanate.

According to the present invention, at least a portion of the polyisocyanate component has an average functionality of 2 to 6, and 5 to 3
It is in the form of a polyisocyanate adduct having an NCO content of 0% by weight. Examples include: 1) DE-PS2, 616,416, EP-OS3,
765, EP-OS 10,589, EP-OS 47,4
52, US-PS 4,288,586, and US-PS
Isocyanurate group-containing polyisocyanates prepared as described in 4,324,879. The isocyanato-isocyanurate generally has an average functionality of from 3 to
3.5 and NCO content 5-30%, preferably 10-10
It has 25%, more preferably 15-25%. 2) Part of the isocyanate group of the diisocyanate is
It is prepared by oligomerization in the presence of a suitable catalyst (for example, a trialkylphosphine catalyst), and contains other aliphatic and / or cycloaliphatic polyisocyanates, especially the isocyanurate group-containing polyisocyanates shown in (1) above. Uretdione diisocyanate which can be used as an additive with isocyanate. 3) U.S. S. Patent No. 3,124,605; 3,35
8,010; 3,644,490; 3,862,97
3, 3,906,126; 3,903,127; 4,0
51,165; 4,147,714; or 4,220,
In accordance with the method disclosed in US Pat.
ctant), for example biuret group-containing polyisocyanates prepared using water, tertiary alcohols, primary and secondary monoamines, and primary and / or secondary diamines. These polyisocyanates are preferably NCO
Content is 18-22% by weight, average NCO functionality is 3-3.
5 4) U.S. S. According to the method disclosed in Patent No. 3,183,112, excess polyisocyanate (preferably diisocyanate) is added to low molecular weight glycol and molecular weight 4
Urethane group-containing polyisocyanates prepared by reacting with less than 00 polyols (e.g., trimethylolpropane, glycerin, 1,2-dihydroxypropane and mixtures thereof). The urethane group-containing polyisocyanate has a most preferred NCO content of 12 to 2
0% by weight, and (average) NCO functionality of 2.5-3.

5) U. S. Patent No. 3,769,31
8. Allophanate group-containing polyisocyanates prepared according to the methods disclosed in 8, 4,160,080 and 4,177,342. The allophanate group-containing polyisocyanate has a most preferred NCO content of 12 to 21% by weight and an (average) NCO functionality of 2 to 4.5. 6) U.S. S. Patent Nos. 5,124,427, 5,20
Polyisocyanates containing isocyanurate groups and allophanate groups, prepared according to the methods described in US Pat. Nos. 8,334, and 5,235,018 (their descriptions being incorporated herein by reference), preferably polyisocyanates. Isocyanates convert these groups to a ratio of monoisocyanurate groups to monoallophanate groups of about 10: 1 to 1:10,
Preferably, it is contained at about 5: 1 to 1: 7. 7) DE-PS1,092,007, US-PS3
152, 162 and DE-OS 2, 504, 400,
Carbodiimide group-containing polyisocyanates prepared by oligomerizing di- or polyisocyanates in the presence of known carbodiimidation catalysts as described in 2,537,685 and 2,552,350. 8) Polyisocyanates containing oxadiazinetrione groups and containing the reaction product of 2 moles of diisocyanate and 1 mole of carbon dioxide. Preferred polyisocyanate adducts are those containing isocyanurate groups, biuret groups, allophanate groups and / or uretdione groups.

Suitable hydrophilic compounds that can be used to stably disperse compounds containing alkoxysilane groups in aqueous media include compounds containing lateral or terminal hydrophilic ethylene oxide units and / or ions or potential ions. A compound containing a group. The ionic or potential ionic group may be either an anionic or cationic group, and is preferably an anionic group. Examples of anionic groups are carboxylate and sulfonate groups, while examples of cationic groups are ammonium and sulfonium groups. The stably dispersed compound is mixed with water and allowed to settle, agglomerate or disperse in either a water-in-oil or oil-in-water emulsion form for a period sufficient to use the dispersion for its intended purpose. It is maintained without releasing. According to the present invention, the compound containing an alkoxysilane group may also comprise a minimum of 2.5% of hydrophilic ethylene oxide units or 100 parts of a compound containing an alkoxysilane group, based on the weight of the compound containing the alkoxysilane group. 5 per minimum
Contains milliequivalent ionic groups. If only hydrophilic ethylene oxide units are used to impart hydrophilicity, they are generally from 5 to 35% by weight, preferably from 10 to 30% by weight, based on the weight of the compound containing alkoxysilane groups.
%, More preferably 12 to 35% by weight.

Suitable compounds for introducing lateral or terminal hydrophilic ethylene oxide units are known and are described in US Pat. S. Patents 3,905,929, 3,920,598, and 4,
190,566 (the disclosures of which are incorporated herein by reference). Preferred hydrophilic components are
Monohydroxy polyether having a terminal hydrophilic chain containing ethylene oxide units. These hydrophilic components comprise monofunctional starting materials, as described in said patent,
For example, it is produced by alkoxylation of methanol or n-butanol using ethylene oxide and another appropriate alkylene oxide (eg, propylene oxide). When only ionic groups are used to impart hydrophilicity, they may have an ionic group content of 1 to 200 meq, preferably 10 to 100 meq, more preferably 25 to 50 meq per 100 g of the compound containing an alkoxysilane group. It is introduced in an amount sufficient to give a milliequivalent. The ionic group can be used to form a corresponding potential ionic group before, during, or after formation of a compound containing an alkoxysilane group,
It is formed by neutralization. The potential ionic group is
If neutralized before the introduction of these compounds, the ionic groups are introduced directly. If neutralization follows compound formation, potential ionic groups are introduced.

Carboxylates, sulfonates and quaternary
Compounds suitable for introducing a nitrogen group are described in US Pat. S. Patents 3,479,310, 4,108,814 and 4,30
3,774, the disclosure of which is incorporated herein by reference. Compounds suitable for introducing a tertiary sulfonium group are described in US Pat. S. No. 3,419,533, which is also incorporated herein by reference. Preferably, the sulfonate groups introduced into the NCO prepolymer are diol sulfonic acid or U.S.P. S. Patent 4,108,814
Diol sulfonate disclosed in US Pat. Neutralizing agents for converting latent ionic groups into ionic groups are described in U.S. Pat. S. It is described in the patent. Within the scope of the present invention, the term "neutralizing agent" is meant to encompass all types of agents useful for converting potential ionic groups into ionic groups.

The compounds containing alkoxysilane groups of the present invention are prepared by reacting the polyisocyanate component with an amino-functional silane and a hydrophilic compound in a ratio of isocyanate groups to isocyanate-reactive groups of about 1: 1. Thus, the resulting product is substantially free of isocyanate groups. The reaction is carried out by adding isocyanate-reactive groups to the polyisocyanate, preferably gradually. The amino-functional silane and the isocyanate-reactive hydrophilic compound may be added continuously or as a mixture, preferably, first, the hydrophilic compound is added,
Subsequently, the aminofunctional silane is added. The reaction for forming a urea group is performed at 10 to 100 ° C, preferably 20 to 80 ° C.
More preferably, the reaction is carried out at 20 to 50 ° C., while the reaction for introducing the isocyanate-reactive hydrophilic compound is performed at 20 to 50 ° C.
It is carried out at 150 ° C, preferably at 50 to 120 ° C, more preferably at 60 to 100 ° C.

The compounds of the present invention are suitable for use in aqueous one-component coating, sealing or adhesive compositions, which include "silane polycondensation", that is, silane groups (Si--O
R) is hydrolyzed and condensed to form a siloxane group (Si-O-
Crosslinking can be achieved by forming Si). When used for this purpose, these compounds may be used as a mixture, together with a suitable acidic or basic catalyst. Examples include acids such as paratoluenesulfonic acid; metal salts such as dibutyltin dilaurate; tertiary amines such as triethylamine, triethylenediamine; and mixtures of these catalysts. Low molecular weight basic aminoalkyltrialkylsilanes, such as those of Formula IV, also promote the cure of the compounds of the present invention. The one-component composition, which may be present as either a water-in-oil or oil-in-water emulsion, is preferably 20-80% by weight, more preferably 30-70% by weight, based on the weight of the one-component composition.
More preferably it has a solids content of 35 to 50% by weight.

The composition may also contain another compound containing an alkoxylane group as a co-reactant of the compound containing an alkoxysilane group, for example, to impart enhanced inorganic properties to the composition. You may. Examples of these co-reactants include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, octyltriethoxysilane and dimethyldiethoxysilane. The composition may also contain known additives such as leveling agents, wetting agents, flow control agents, anti-skinning agents, defoamers, fillers (eg, silica, aluminum silicates and high boiling waxes), viscosity modifiers, Plasticizers, pigments, dyes, UV absorbers,
It may also contain stabilizers against thermal and oxidative degradation.

The one-component composition may be applied to any desired support, such as wood, plastic, leather, paper, fabric, glass, ceramics, plaster, brick, metal and concrete. They can be prepared by standard methods such as spray coating, knife coating.
g), may be applied by flow coating, casting, dip coating or roll coating. The coating composition may be a clear or colored lacquer. The one-component compositions can be cured at ambient temperature, but for optimal properties these compositions are cured at elevated temperatures of 80-250 ° C, preferably 120-180 ° C. If there is a co-reactant in the one-component composition,
It can be used to modify properties and resulting products. For example, coatings prepared from these compositions have different performance characteristics, such as higher hardness, than coatings prepared from compositions that do not contain these co-reactants. The invention is further described in the following examples, which are not intended to limit the invention. All parts and percentages are by weight unless otherwise indicated.

[0026]

EXAMPLES Polyisocyanate 1 Prepared from 1,6-hexamethylene diisocyanate and having an isocyanate content of 21.6%, a monomeric diisocyanate content of <0.2% and a viscosity at 20 ° C. of 3000 mPa.s. s isocyanurate group-containing polyisocyanates (Desmodu from Bayer)
r N3300). Polyether 1 Polyethylene oxide monol prepared by ethoxylation of methanol and having a molecular weight of 750 (Unio).
n commercially available as Carbowax 750 from Carbide). Polyether 2 Polyethylene oxide monol prepared by ethoxylation of methanol and having a molecular weight of 550 (Unio
n commercially available from Carbide as Carbowax 550).

Example 1 Preparation of N- (3-trimethoxysilylpropyl) aspartic acid diethyl ester 1438 parts (8.27 equivalents) of 3-aminopropyltrimethoxysilane were added to an agitator, thermometer, nitrogen inlet,
And a 5 L flask equipped with an addition funnel with condenser. 1423.2 parts (8.27 equivalents) of diethyl maleate were added dropwise over 2 hours. The reactor temperature was maintained at 25 ° C. during the addition. After maintaining the reactor at 25 ° C. for an additional 5 hours, the product was poured into a glass vessel and sealed with a nitrogen blanket. After one week, the unsaturation value was 0.6, indicating that the reaction was ~ 99%
Indicates completion. The product [N- (3-trimethoxysilylpropyl) aspartic acid diethyl ester]
Is 11 mPa. s.

Example 2 Preparation of water-dispersible resin 1 195 parts (1 equivalent) of polyisocyanate 1 were added at ambient temperature to a three-necked 5 L equipped with an agitator, thermometer, nitrogen inlet, and addition funnel with condenser. Added to round bottom flask. The reaction flask was heated to 60C. 90
Parts (0.12 equivalents) of polyether 1 (heated to 60 ° C.)
Was added to the reaction flask via an addition funnel over 20 minutes to control the exotherm of urethane formation. After the reaction was maintained at 60 ° C. for 4 hours, the isocyanate content was 13.8% (theoretical NCO content: 13.0%). The reaction was cooled to 40 ° C. and 341 parts (0.93 equivalents) of N- (3-trimethoxysilylpropyl) aspartic acid diethyl ester were added via an addition funnel to control the exotherm. The reaction was heated for another 3 hours until no isocyanate groups remained as determined by IR spectroscopy. After cooling to room temperature, the resulting product has a mPa. s. 20 parts of this product were combined with 10 parts of water and stirred at high speed with a lightning mixer. A stable dispersion was obtained. A cured coating could be prepared by the addition of a water-compatible catalyst.

Example 3 Preparation of water-dispersible resin 2 195 parts (1 equivalent) of polyisocyanate 1 were added at ambient temperature to a three-necked 5 L equipped with an agitator, thermometer, nitrogen inlet, and addition funnel with condenser. Added to round bottom flask. The reaction flask was heated to 60C. 8
2.5 parts (0.15 equivalents) of polyether 2 (heated to 60 ° C.) were added to the reaction flask via an addition funnel over 20 minutes to control the exotherm of urethane formation. The isocyanate content after maintaining the reaction at 60 ° C. for 4 hours was 14.4% (theoretical NCO content 14.1%). The reaction was cooled to 40 ° C and 312 parts (0.
85 equivalents) of N- (3-trimethoxysilylpropyl)
Diethyl aspartate was added via an addition funnel to control the exotherm. The reaction was heated for another 3 hours until no isocyanate groups remained as determined by IR spectroscopy. After cooling to room temperature, the product obtained is 2
At 5 ° C., mPa. s.
20 parts of this product were combined with 10 parts of water and stirred at high speed with a lightning mixer. A stable dispersion was obtained.
A cured coating was prepared as described in Example 5.

Example 4 Preparation of water-dispersible resin 3 195 parts (1 equivalent) of polyisocyanate 1 were added at ambient temperature to a three-neck 5 L equipped with an agitator, thermometer, nitrogen inlet, and addition funnel with condenser. Added to round bottom flask. The reaction flask was heated to 60C. 24
Addition of 2 parts (0.66 equivalents) of N- (3-trimethoxysilylpropyl) aspartic acid diethyl ester resulted in an exotherm of 60 ° C. After cooling the reaction mixture, 18
1.5 parts (0.33 equivalents) of polyether 2 (heated to 60 ° C.) was added to the reaction flask as quickly as possible. The mild exotherm raised the temperature to 60 ° C. IR
The reaction was maintained at 60 ° C. for 4 hours until no isocyanate groups remained as determined by spectroscopic analysis. After cooling to room temperature, the resulting product has a mPa.
s. 20 parts of this product were combined with 10 parts of water and stirred at high speed with a lightning mixer. A clear solution was obtained. A cured coating could be prepared by the addition of a water-compatible catalyst.

Example 5 Preparation of Coating Water-dispersible resin 2 was dispersed in water with a high-speed mixer and mixed with the catalyst. The resulting mixture was used to prepare a film. The film was drawn down on cold rolled steel at a wet film thickness such that the dry film thickness was 1-1.5 mil, then cured at 130 ° C. for 30 minutes. The amounts of the various components and the properties of the resulting coating are shown in the table below.

[0032]

[Table 1] Block acid catalyst based on A-p-toluenesulfonic acid B-p-toluenesulfonic acid and a branded amine (commercially available from King Industries as Nacure 2558) C-Phenyl acid phosphate (PA75 from Albright and Wilson) Commercially available) Blocked acid catalyst based on D-dinonylnaphthalene monosulfonic acid and a trademarked amine (commercially available from King Industries as Nacure 1323)

The MEK double rub was measured by wetting each panel with methyl ethyl ketone and rubbing each panel up to 100 times. Double rubs consist of rubbing the coated panel back and forth once. A value less than 100 is the number of double rubs before the coaching is broken. Pencil hardness was measured according to ASTM D-3363.
The order of hardness is from 6B to 1B, HB,
F, 1H to 8H.

While the present invention has been described in detail for purposes of illustration, it is merely therefor and those skilled in the art will depart from the spirit and scope of the invention except as defined by the appended claims. It should be understood that changes can be made without modification.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) // C08G 18/38 C08G 18/38 Z 18/77 18/77 Z 18/79 18/79 A C09D 175 / 04 C09D 175/04 C09J 175/04 C09J 175/04 (72) Inventor Richard Earl.・ Roessler 15090 Wetzhuks, Pennsylvania United States, Hillcrest Cycle 863 (72) Inventor Rututsu Schyumar Stake Germany 50676 Cologne Day 50676 Cologne, Schühl-Nurgasse 45

Claims (14)

[Claims] 1. A chemical having an alkoxysilane group content (Si, calculated as molecular weight 28) of 1 to 6% by weight, based on the weight of the compound, and sufficient to form a stable dispersion using water. A substantially isocyanate group-free compound containing a partially introduced hydrophilic group, the alkoxysilane group comprising: a) a minimum average functionality of 2.4 and at least 50
A polyisocyanate component containing, by weight, a polyisocyanate adduct; b) a compound of formula I Wherein, X is the same or different and is an organic group inert to isocyanate groups below 100 ° C., provided that at least one of these groups is an alkoxy group, R ₁ is a 100 ° C. or less And n is an integer of 1 to 8], and the compound is introduced as a reaction product with an amino compound. 2. The amino compound of the formula III [Wherein, Z represents COOR ₅ or an aromatic ring, R ₂ and R ₅ are the same or different and are an organic group inert to an isocyanate group at 100 ° C. or lower, and R ₃ and R ₄ are
The same or different and is hydrogen or an organic group which is inactive to an isocyanate group at 100 ° C. or lower]. 3. X represents the same or different alkyl or alkoxy group having 1 to 4 carbon atoms, Z represents COOR ₅ , R ₂ and R ₅ are the same or different and 1 to 4 It represents an alkyl group having 9 carbon atoms, R ₃ and R ₄ represents hydrogen, n is an integer of 2 to 4, the compounds of claim 2. Wherein X are the same or different, represent an alkoxy group having 1 to 4 carbon atoms, Z is, represents COOR _5, R ₂ and R ₅ are the same or different, and methyl, ethyl or butyl, R ₃ and R ₄ represents hydrogen, n is 3, the compound of claim 2. 5. The polyisocyanate component has a minimum average functionality of at least 2.8 and at least 70
The compound of claim 1 which contains by weight polyisocyanate adduct. 6. The polyisocyanate component has a minimum average functionality of at least 2.8 and at least 70
3. A compound according to claim 2 which contains by weight polyisocyanate adduct. 7. The polyisocyanate component has a minimum average functionality of at least 2.8 and at least 70
4. A compound according to claim 3 containing by weight polyisocyanate adduct. 8. The polyisocyanate component has a minimum average functionality of at least 2.8 and at least 70
5. A compound according to claim 4 containing by weight polyisocyanate adduct. 9. The water-dispersible compound according to claim 5, wherein said polyisocyanate adduct contains isocyanurate groups, biuret groups, allophanate groups and / or uretdione groups. 10. The water-dispersible compound according to claim 6, wherein said polyisocyanate adduct contains isocyanurate groups, biuret groups, allophanate groups and / or uretdione groups. 11. The water-dispersible compound according to claim 7, wherein the polyisocyanate adduct contains an isocyanurate group, a biuret group, an allophanate group and / or a uretdione group. 12. The water-dispersible compound according to claim 8, wherein said polyisocyanate adduct contains isocyanurate groups, biuret groups, allophanate groups and / or uretdione groups. 13. A one-component coating, sealant or adhesive composition wherein the binder comprises the water-dispersible compound of claim 1. 14. A one-component coating, sealant or adhesive composition wherein the binder comprises the water-dispersible compound of claim 1 and further a compound containing an alkoxysilane group.